Homogeneous Catalytic Carbonylation of Nitroaromatics. 8. Kinetic and Mechanistic Studies of the Carbon-Nitrogen Bond and Product Forming Steps from Ru(Ph2PCH2CH2PPh2)(CO)2[C(O)OCH3]2: The Turnover Limiting Reactions in the Catalytic Cycle

1994 ◽  
Vol 116 (9) ◽  
pp. 3792-3800 ◽  
Author(s):  
Jerry D. Gargulak ◽  
Wayne L. Gladfelter
Keyword(s):  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Catalytic Carbonylation ◽  
Nitrogen Bond

Synthesis of diaryldifluoromethanes by Pd-catalyzed difluoroalkylation of arylboronic acids

2015 ◽  
Vol 2 (1) ◽  
pp. 38-41 ◽  
Author(s):  
Ji-Wei Gu ◽  
Wen-Hao Guo ◽  
Xingang Zhang
Keyword(s):  
Electron Transfer ◽  
Catalytic Cycle ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Mechanistic Studies ◽  
Arylboronic Acids

The first example of Pd-catalyzed aryldifluoromethylation of arylboronic acids with readily available aryldifluoromethyl bromides has been described. Preliminary mechanistic studies revealed that a Pd(0)Ln-initiated single electron transfer (SET) pathway is involved in the catalytic cycle.

H2 evolution by a cobalt selenolate electrocatalyst and related mechanistic studies

2017 ◽  
Vol 53 (53) ◽  
pp. 7306-7309 ◽  
Author(s):  
Courtney A. Downes ◽  
Joseph W. Yoo ◽  
Nicholas M. Orchanian ◽  
Ralf Haiges ◽  
Smaranda C. Marinescu
Keyword(s):  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
H2 Evolution

[Co(bds)2][nBu4N] (where bds = 1,2-benzenediselenolate) was identified as an electrocatalyst for H2 evolution. Mechanistic studies indicate that with acid a protonated oligomeric {[Co(bds)2(H)x]x−1}m is formed, which was found to reenter the catalytic cycle and generate H2.

scholarly journals Manganese-Catalyzed Ammonia Oxidation into Dinitrogen

2020 ◽  
Author(s):  
Hiroki Toda ◽  
Kazunari Nakajima ◽  
Ken Sakata ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Ammonia Oxidation ◽  
Nucleophilic Attack ◽  
Mechanistic Studies ◽  
Oxidative Conversion ◽  
Functional Theory ◽  
Metal Catalyzed ◽  
Nitrogen Bond

Base metal-catalyzed oxidative conversion of ammonia into dinitrogen is a promising process to utilize ammonia as an energy carrier. In this study, we report the manganese-catalyzed ammonia oxidation under chemical and electrochemical conditions. Mechanistic studies including density functional theory (DFT) calculations suggest that a nucleophilic attack of ammonia on manganese nitrogenous complexes occurs to form a nitrogen–nitrogen bond leading to dinitrogen.<br>

scholarly journals Manganese-Catalyzed Ammonia Oxidation into Dinitrogen

2020 ◽  
Author(s):  
Hiroki Toda ◽  
Kazunari Nakajima ◽  
Ken Sakata ◽  
Yoshiaki Nishibayashi
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Ammonia Oxidation ◽  
Nucleophilic Attack ◽  
Mechanistic Studies ◽  
Oxidative Conversion ◽  
Functional Theory ◽  
Metal Catalyzed ◽  
Nitrogen Bond

Base metal-catalyzed oxidative conversion of ammonia into dinitrogen is a promising process to utilize ammonia as an energy carrier. In this study, we report the manganese-catalyzed ammonia oxidation under chemical and electrochemical conditions. Mechanistic studies including density functional theory (DFT) calculations suggest that a nucleophilic attack of ammonia on manganese nitrogenous complexes occurs to form a nitrogen–nitrogen bond leading to dinitrogen.<br>

scholarly journals The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)–O Arylation

2020 ◽  
Author(s):  
Reginald Mills ◽  
John. J. Monteith ◽  
Sophie Rousseaux
Keyword(s):  
Cyclopropane Ring ◽  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Design And Optimization ◽  
Redox Active ◽  
Leaving Group

<div><p>The ability to understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp<sup>3</sup>)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp<sup>3</sup>)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active, and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.</p></div>

scholarly journals The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)–O Arylation

2020 ◽  
Author(s):  
Reginald Mills ◽  
John. J. Monteith ◽  
Sophie Rousseaux
Keyword(s):  
Cyclopropane Ring ◽  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Design And Optimization ◽  
Redox Active ◽  
Leaving Group

<div><p>The ability to understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp<sup>3</sup>)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp<sup>3</sup>)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active, and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.</p></div>

Boron-Catalyzed Hydrogenative Reduction of Substituted Quinolines to Tetrahydroquinolines with Hydrosilanes

Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2396-2400 ◽  
Author(s):  
Sehoon Park ◽  
Sukbok Chang ◽  
Narasimhulu Gandhamsetty
Keyword(s):  
Initial Step ◽  
Reducing Agents ◽  
Catalytic Cycle ◽  
Transfer Hydrogenation ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Substituted Quinolines ◽  
Optimized Conditions ◽  
Hydroxy Groups

A metal-free procedure for the hydrogenative reduction of substituted N-heteroaromatics has been developed by using hydrosilanes as reducing agents. The optimized conditions were successfully applied to the reactions of quinolines, quinoxalines, and quinoline N-oxides. They were also effective for the reduction of quinolines bearing amino or hydroxy groups, where H2 was evolved through dehydrogenative silylation of the amine or hydroxy moieties. Preliminary mechanistic studies revealed that the initial step in the catalytic cycle involves 1,4-addition of the hydrosilane to the quinoline to give a 1,4-dihydroquinoline; this is followed by (transfer) hydrogenation to deliver the tetrahydroquinoline as the final product.

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